Methods for collection fractions of mixtures, suspensions, and solutions of non-polar liquids

ABSTRACT

A polar liquid mixture containing suspended or dissolved particles or solute is exposed to air or a hydrophilic surface. An exclusion zone having a reduced concentration of particles or solute is formed in the polar liquid adjacent to the interface with air or the hydrophilic surface. One or more fractions of purified polar liquid and/or concentrated particles or solute are collected. A sensor can provide feedback to the collector.

RELATED APPLICATIONS

This application is a Continuation-in-Part of, and claims priority toU.S. patent application Ser. No. 12/363,189, filed on Jan. 30, 2009, NowU.S. Pat. No. 7,819,259B2 entitled “Separating Components of AqueousMixtures, Suspensions, and Solutions”, naming Gerald H. Pollack as aninventor; which is a Continuation-in-Part of, and claims priority toU.S. patent application Ser. No. 11/623,719, filed on Jan. 16, 2007, NowU.S. Pat. No. 7,793,788 B2, entitled “Separating Components of AqueousMixtures, Suspensions, and Solutions”, naming Gerald H. Pollack as aninventor; which claims priority to U.S. Provisional Patent ApplicationNo. 60/743,135, filed on Jan. 17, 2006, entitled “Separating Componentsof Aqueous Mixtures,” naming Gerald H. Pollack as an inventor; thedisclosures of which are, to the extent not inconsistent with thedisclosure herein, incorporated herein by reference.

SUMMARY

Systems and methods are described for separating and/or collectingfractions of fluids including components of mixtures, suspensions, andsolutions in polar liquids. In one embodiment, an apparatus flows anaqueous mixture over a hydrophilic surface to form a first region ofpurified water and a second region of at least one concentratednon-aqueous component. The apparatus can draw off either the purifiedwater or the concentrated non-aqueous components. In one embodiment, anarray of tubules performs the differential extraction. In anotherembodiment, various hydrophilic and/or hydrophobic surfaces are disposedin multiple differential extractors and some effluents may be recycledto perform complex assaying and separation. In another embodiment anapparatus can draw off purified water just beneath an air-waterinterface.

According to an embodiment, an apparatus for collecting a fraction of amixture, suspension, or solution of a polar liquid includes a firstcollector configured to collect a fraction of a mixture, suspension, orsolution of a polar liquid at a selected distance at or away from aninterface between the polar liquid and air or a hydrophilic surface; anda structure configured to hold the first collector at the selecteddistance. A first fraction collected from a first region at a firstproximate distance at or away from the interface includes substantiallypure polar liquid. A second fraction collected at a second distaldistance away from the interface in the second region includes a anincreased concentration of a solute or particle component compared tothe first fraction.

According to another embodiment, a method for collecting a fraction of apolar liquid mixture, suspension, or solution includes receiving,establishing, or accessing a volume of a polar liquid mixture,suspension, or solution; allowing an exclusion zone to form adjacent toan interface between the polar liquid mixture, suspension, or solutionand air or a hydrophilic surface; and collecting a fraction of the polarliquid mixture, suspension, or solution at or at a selected distancefrom the air or hydrophilic surface.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram of an exemplary differential extractor forseparating components of aqueous mixtures, according to an embodiment.

FIG. 2 is a diagram of exemplary dimensions of one implementation of thedifferential extractor of FIG. 1, according to an embodiment.

FIG. 3 is a diagram of an exemplary system for separating components ofaqueous mixtures, according to an embodiment.

FIG. 4 is a diagram of concentration gradients achieved by an exemplarysystem, according to an embodiment.

FIG. 5 is a diagram of swelling of an exemplary material used in adifferential extractor, according to an embodiment.

FIG. 6 is a diagram of exemplary solute exclusion, according to anembodiment.

FIG. 7 is a diagram of growth of an exemplary exclusion zone over time,according to an embodiment.

FIG. 8 is a diagram of exemplary separation of a protein from an aqueousmixture, according to an embodiment.

FIG. 9 is a diagram of exemplary separation of a dye from an aqueousmixture, according to an embodiment.

FIG. 10 is a diagram of an exemplary interface between a gel exclusionsurface and a collector, according to an embodiment.

FIG. 11 is a diagram of an exemplary exclusion zone over time and atdifferent distances along an exclusion surface, according to anembodiment.

FIG. 12 is a diagram of an exemplary extraction apparatus to interfacewith a gel exclusion channel, according to an embodiment.

FIG. 13 is a diagram of an exemplary array of differential extractors,according to an embodiment.

FIG. 14 is a flow diagram of an exemplary method of separatingcomponents of aqueous mixtures, according to an embodiment.

FIG. 15 is diagram of an exemplary exclusion zone just beneath anair-water interface, according to an embodiment.

FIG. 16 is a diagram illustrating principal features of an apparatus forcollecting a fraction of a mixture, suspension, or solution of a polarliquid, according to an embodiment.

DETAILED DESCRIPTION

Overview

Embodiments according to this disclosure describe methods andapparatuses for collecting fractions of mixtures, suspensions, andsolutions of polar liquids. For example, the polar liquid can consistessentially of water. Other polar liquids that form an exclusion zoneadjacent to an interface with a hydrophilic surface or air may behavesimilarly and have fractions of mixtures, suspensions, or solutionscollected.

Illustrative examples relating to the collection of fractions from waterare described as embodiments herein, but similar apparatuses and methodsmay be made and performed using similar approaches with other polarfluids. The term “aqueous mixture” will be used herein to represent anillustrative aqueous mixture, suspension, or solution. To collectfractions, the aqueous mixture is exposed to a hydrophilic surface, suchas the inside of tubes made of hydrophilic materials. A regioncorresponding to a “purified water” fraction forms near the hydrophilicsurface in which one or more solutes or other non-aqueous components arepartially or entirely excluded. Hence, the hydrophilic surface is alsoreferred to herein as an “exclusion surface.” Likewise, a regioncorresponding to a “concentrated solute” fraction forms “away from” theexclusion surface. Thus, the gradient caused by the exclusion surfacecan be exploited to obtain fractions of water such as purified water ora concentrated phase of a non-aqueous component.

Such aqueous mixtures include salt solutions, colloids, suspensions,waste water, bodily fluids, mining tailings, etc., that is, most anycombination of water and another compound or substance. Non-aqueouscomponents of an aqueous mixture can include organic and inorganicsalts, biomatter, pathogens, bacteria etc., and many other solids andsemi-solids. For example, the exemplary techniques to be describedherein can separate microspheres that are similar in size to bacteria toeasily obtain a 20:1 separation.

In one implementation, an exemplary method removes salts from water toobtain efficient desalination. The salts to be separated can includesodium chloride, seawater salts, components of buffer solutions, andmany other salts and ionic compounds. Hence, exemplary methods canseparate ionic (charged) components from water mixtures, or can separateneutral, non-ionic species from water mixtures too.

From another perspective, the subject matter to be described canconcentrate dissolved or suspended species from aqueous solutions. Thatis, instead of pure water being the only desired product, an exemplarymethod can be used to concentrate the non-aqueous components of anaqueous mixture. This can be useful in many manufacturing processes andin the clinical lab, e.g., for diagnosing medical conditions via bloodwork and other physiological tests that involve bodily or cellularfluids. The exemplary methods described herein can be used to separateand/or concentrate salts, pathogens, contaminants, dyes, organic andinorganic species, etc., from aqueous mixtures. Solute size can be assmall as a few nanometers (e.g., molecular weight of approximately 300).

In one implementation, multiple separation stages are performed inseries, including, for example, a cascade of multiple similar stagesiterated to amplify the effect, as well as variegated stages fordifferent materials. Thus, process flow may follow a tree structure orflow diagram analogous to complex stages of a chemical synthesis orpurification, in which different components are separated orconcentrated at different times and in different quantities by differentimplementations or instances of the exemplary exclusion surface. Thesuccession of stages allows an exemplary process to exclude more typesof solutes from an increasingly purer aqueous mixture. The successioncan also improve the purification of a single material, e.g., toautomatically obtain a super pure product in the lab. Moreover, a usercan specify which non-aqueous species are to be separated out orconcentrated from an aqueous mixture.

Exemplary Process

We found that many solutes were excluded from a region adjacent tohydrophilic surfaces. Included among the excluded species weremicrospheres of various size, erythrocytes, proteins, and even smallmolecular weight dyes. Salts also appeared to be excluded. The exclusionzone varied in size, but in one implementation was several hundredmicrometers wide. Given the large size of this zone, and the exclusionof many solutes, we discovered that the exclusion zone contained “pure”water, which could then be harvested. The formation of the exclusionzone was similar to the formation of ice—which crystallizes to theexclusion of foreign materials in its molecular structure.

In general, negatively charged surfaces exclude negatively chargedsolutes, and positively charged surfaces exclude positively chargedsolutes. So, for many different solutes, a surface can be selected thatwill exclude solutes from a region of pure or purer water. Bacteria,viruses, etc., fall into size and charge domains as solutes that wetypically tested, so these too can be excluded from the region ofpurified water. Biological specimens, such as red blood cells, were alsoexcluded from this region. It is worth noting that negatively chargedsurfaces do, in general, exclude negatively charged solutes; however,some positively charged solutes are excluded as well. Similarly,positively charged surfaces generally exclude positively chargedsolutes, but also some negatively charged solutes as well.

Flow Profile Measurements

An initial issue to be tested was whether the water in such an exclusionzone near a surface was or was not bound to the nucleating surface(i.e., a gel, polymer, or other exclusion surface). If the water adheredtightly, then removal would not be easily possible. To pursue thisquestion we used polyacrylic acid gels, with characteristic dimensionsof several centimeters, containing a 2-mm channel. Because the gel wasclear, the channel could be visualized using an optical microscope.Microsphere suspensions were forced through the channel under pressure.At the entryway, microspheres were uniformly distributed across thecross section. Farther along the channel, an exclusion zone developed:the annulus was clear, while the core region contained concentratedspheres. Still farther along, the clear annulus grew at the expense ofthe core, and ultimately, after several centimeters, the relativedimensions of annulus and core no longer changed.

To assess whether annular water adhered to the gel surface, we measuredvolume flow at intervals of several millimeters along the channel. Theprofile could be measured only in the core, where microspheres werepresent, and not in the annulus, where there were no markers. Thus, thecomplete profile could be measured near the entryway, while only partialprofiles could be measured farther along. Each profile was integrated togive volume flow. Thus, we could obtain volume flows in themicrosphere-containing zones at intervals along the channel. If theintegrated flows were equal at all points, then we would have concludedthat the annular regions were adherent; only the microsphere-containingregions flowed. By contrast, we found that the integrated profilesdiminished significantly with distance along the channel. This meantthat volume flow in the microsphere zones decreased progressively alongthe channel. Or, in other words, some of the flow had to come from theclear annulus. We established that the annular region did, indeed, flow(at least in part), making possible the exemplary techniques.

Apparatus for Solute Separation

As shown in FIG. 1, an exemplary “differential extractor” 100 separatesa solution into concentrated and dilute (clear) fractions. The principleof the extraction is also illustrated in FIG. 1. A homogenousmicrosphere suspension 102 enters a NAFION tube 104 at one end (DuPontCorporation, Wilmington, Del.). NAFION is a Teflon-like polymer withexposed sulfonate groups, used in fuel cells, actuators, and otherapplications. In one implementation, NAFION was found to be an idealexclusion surface and will be referred to herein as a representativematerial for the exemplary exclusion surface, although other materialscan also be used for the exclusion surface. As the solution travelsthrough the NAFION tube 104, the microspheres 102 migrate from the walls106 of the tube 104 and gather in the core region 108. Clear water fromthe exclusion zone 110 and microsphere-containing water 112 pass throughdifferent channels of the extractor 100, and are then collected. In oneimplementation, the differential extractor 100 is used to extract clearwater.

In FIG. 2, the dimensions of one implementation of the exemplarydifferential extractor 100 are given. An elevation view 202 shows thetwo different channels that draw off the concentrated and dilutedproducts of the separation. Of course, either the concentrated ordiluted products of the extractor 100 can be subjected to subsequentinstances of the extractor 100 to provide further concentration ordilution of the particular product. The concentration branch or thedilution branch of the extractor 100 can even be looped back to theinput of the NAFION tube to recycle the particular product multipletimes through the same extractor 100.

Another implementation of an extraction schema is shown in FIG. 3. Pump“1” 302 and Pump “2” 304 reduce the pressure in the peripheral channeland the center channel, respectively, to facilitate collection. Pressurereduction in the channels results in inflow of solution into thechannels with linear velocity proportional to the negative pressuregenerated by each pump. The negative pressures can be adjusted so thatthe linear velocity is equal in both channels. The concentrated anddilute solutions can be collected in different syringes. Importantly, inthis implementation, the tube 104 itself can be immersed in the, e.g.,microsphere 102 (or salt) solution. Hence, the initial concentration inthe solution outside the tube 104 is the same as that of the solutioninside.

Three differential extractors 100 are described as examples. In oneimplementation, the extractor 100 is constructed with glue. Brassbushings are used for maintaining tube concentricity. The proximal endof the extractor 100 is initially flush. This implementation shows thatthe exemplary extractor 100 can be made of diverse materials, as long asthey are impervious to the components being separated.

In another implementation, the extractor 100 can be constructed fromstainless steel tubing, and overall lengths can be increased toaccommodate some different features. In this case, the extractor 100incorporates an extension sleeve on the outer tubing to increaseextraction efficiency.

In yet another implementation, the differential extractor 100 has largerdiameter stainless steel tubing to accommodate a relatively largerNAFION tubing 104 that, especially effective for some applications. Forexample, construction can be carried out with low temperature silversolder, and concentricity can be maintained by dimpling the outer tube.The distance between inner and outer tube, the annulus, can beapproximately 0.1 mm. Also, the central tube, used to collect highlyconcentrated microspheres, can be extended out 0.5 mm at the proximalend. This makes it possible to visualize the extraction processmicroscopically. This, in turn, may allow flows to be regulated in asensitive manner to match the relative size of the exclusion zones. Inone implementation, the smaller the exclusion zone 110, the largershould be the difference of flow in order to achieve good separation.Given the availability of a sensitive manner of adjusting flows, 10-20times concentration difference can be obtained (e.g., see images in FIG.1).

The particular geometry and materials employed in the exemplaryextractor 100 can be varied to improve results for a particularapplication. For instance, a polyacrylic-acid gel may also be used asthe exclusion surface.

In one implementation, particles in the micron-size range can beseparated out of water using the exemplary techniques. Depending onrefinement of the implementation, the extractor 100 may achieve a 10:1or 20:1 concentration difference ratio between purified water andmicrosphere enriched output. With multiple extraction stages in series,e.g., using different extraction surfaces, superb separation ratios areachievable. Separating (micron-sized) pathogens is therefore possible.

Spectrophotometric Studies

In one implementation, relatively slow flow in the NAFION tube ismaintained in order to prevent turbulence, which increases reliabilityand may be used in circumstances in which the speed of extraction is ofsecondary importance. For example, in a model implementation, 100 ml ofconcentrated and 10 ml of dilute solution were collected over 10-12hours.

An exemplary method was adopted to detect even small differences inconcentration. We found that spectrophotometer readings gave the firstsign of successful separation, albeit sometimes they were very small.After two fractions were collected, absorption spectra were obtained forconcentrated and dilute species using a UV-VIS spectrometer. Examples ofabsorption curves are shown in FIG. 4, where the upper curve correspondsto the concentrated fraction and the lower curve corresponds to thepurified fraction. The result corresponds to one implementation, inwhich the separation ratio was relatively low, approximately 1:2 or 1:3.Early development of the separation principle also showed that thespectrophotometric method could be used as a sensitive detector of evensubtle differences between fractions.

Microsphere Counting

After the spectrophotometric approach for detecting a concentrationgradient was pursued, an initial gel implementation was replaced by theNAFION tubing described above, and improved extractors were therebydeveloped. As development of exemplary methods progressed, theconcentration difference between fractions grew sufficiently large, upto 20:1, that it could be seen by the naked eye, or measured accuratelyby use of a microscope.

Thin layers of the concentrated and dilute fractions were thereforecreated and viewed with a microscope. Since the microscope has a finitedepth of field, direct counting of microspheres in the field gives thenumber within some fixed volume, i.e., the concentration. By comparingthe number of the microspheres in the respective fractions, theconcentration difference could be ascertained. In one phase ofdevelopment, approximately ten experiments were carried out. The layersof solution were of the same thickness, ca. 0.1 mm. The area was 1-2square cm.

One result obtained using this approach showed a separation of betweenapproximately 10:1 to 20:1. However, in this implementation the ratiowas strongly dependent on the desired collection rate. If water from theouter annulus was drawn very slowly, we estimate that, practically, itwill be possible to obtain separation coefficients of 100:1 or evenhigher—mainly because the exclusion zone never contains microspheres,even when the microsphere concentration is raised to high values.

Further Experimental Details

Initial microsphere concentration was 2.84×10exp6 particles/ml in mostexperiments during development. In the photographs presented, theinitial solution concentration was 1.13×10exp7 particles/ml. POLYBEADCarboxylate 2.0 μm microspheres were used and were diluted in distilledwater (Polysciences, Inc., Warrington, Pa.).

The extraction speed, i.e., the volume flow inside the NAFION tube, was1 ml/hour if the experiment was conducted overnight or 4-5 ml/hourduring the daytime. With this speed, we collected 2 ml of dilutesolution per 10 ml of concentrated solution; generally this took 2.5hours.

Salt Separation & Small Osmolality Difference Measured with theOsmometer

After experiments with the microspheres were carried out, we beganexperiments with salt solutions (e.g., sodium chloride, ˜500 mmol/l).Initially, these experiments were carried out the same way as with themicrospheres solution. The experimental setup was similar or the same,although a microscope was not used for adjusting the flow velocitybecause no microsphere markers were present. Of seven exampleexperiments conducted, four showed osmolality difference between“concentrated” and “dilute” fractions. Experimental results for theseare shown in the Table (1) below.

TABLE 1 No of Experiment No of Measurements “Diluted” SolutionConcentration, mmol/l (Dc) “Concentrated” Solution Concentration, mmol/l(Cc) Cc-Dc $\frac{{Cc} - {Dc}}{Dc}100\%$ Average % 1 1 466 499 33 7.08%7.53% 2 467 505 38 8.14% 3 475 510 35 7.37% 2 1 673 733 60 8.92% 7.81% 2687 733 46 6.70% 3 690 744 54 7.83% 3 1 630 651 21 3.33% 3.10% 2 632 65119 3.01% 3 644 663 19 2.95% 4 1 964 1001 37 3.84% 5.23% 2 984 1032 484.88% 3 1005 1075 70 6.97%

The repeatability of the salt solution separation measurements in eachexperiment was significantly high. In some circumstances, it may be thatthe exclusion zone is considerably smaller with high concentrations ofsalt than with microspheres in pure water; hence, the outer annuluscollected some pure water and mostly salt water. A collector withsmaller annulus can be built for salt exclusion.

NAFION Tube Swelling Experiments

We observed that sometimes, some grades of NAFION swell less in saltsolutions than in pure water. The higher the osmolality, the less theNAFION swells. Thus, one possibility is that salt ions are held by thewater molecules—they do not enter the NAFION polymer, either within theNAFION wall itself, or immediately around the wall. In other words, theymay not penetrate into the exclusion zone.

We hypothesized that if salt ions do not enter in or around the polymernetwork, then, as the NAFION swells, the salt concentration of thesolution used to swell the NAFION becomes higher. This hypothesis wastested in the following experiment. First, a salt solution of knownconcentration was pumped inside the dry NAFION tube. The outside of thetube was dry. After approximately 10 minutes the NAFION tube swelled, atthe expense of the solution inside. Then, the remaining solution waspumped out of the NAFION tube, and its osmolality was measured. Threeexperiments were carried out. Each time, there was an osmolalityincrease following swelling (see Table (2) below). Hence, the resultssupport the hypothesis: it appears that salt is excluded from around theNAFION polymer; only water appears to enter.

To check this result, calculations were made based on the assumptionthat only water molecules enter the NAFION polymer network. The NAFIONtube was weighed as shown in FIG. 5, before and after swelling, andtherefore the amount of water that enters was known. With this data, itcan be calculated what the predicted concentration increase in thetube's lumen should be. Table (2) below shows excellent agreement,within several percent. Hence, the assumption that no salt entersin/around the NAFION polymer was tentatively validated.

Controls were made to test the possibility that the observed increase ofosmolality might arise artifactually, from some chemicals diffusing outof the NAFION. This possibility was tested by swelling the NAFION indeionized water instead of salt water. The solution removed from theNAFION tube showed no measurable increase of osmolarity. Hence, theincrease of osmolality in Table (2) below was considered to have arisenfrom salt, excluded from the NAFION network.

There may be a distinction between the water lying within, andimmediately outside of, the NAFION tubing. Both are in the vicinity ofpolymer. If they behave similarly, then salt is deemed to be definitelyabsent from the exclusion zone. If not, then it is possible that thesalt is excluded only from the water fraction lying within the tubing,but not from the fraction adjacent to it.

TABLE (2) Solution Solution Predicted concentration concentrationSolution before NAFION after NAFION concentration swelled (mM) swelled(mM) (mM) % error 398 484 470 2.3 401 475 455 4.2 422 480 464 3.3Alternate Embodiments

When experimenting with microsphere suspensions, we found that it ispossible to draw small amounts of microsphere-free water from theexclusion zone. Practical success depends on how small the exclusionzone is with salt present. In the case of salt solutions, a NAFION tubecan be used to create an exclusion zone. Then, a micropipette with tipdiameter of, for example, 10 μm can be used to suck water via a tinyopening adjacent to the NAFION surface. By repeating this many times ina model setup, it is possible to collect solution, e.g., enough solutionfor osmolality measurements. Alternatively, a single step sample can beused to collect a very small amount of water. Speed of evaporation ofthis solution can be compared with evaporation of the solution takenfarther from the NAFION surface. Practically salt-free water shouldevaporate more rapidly than relatively salty water.

Another measurement approach uses a sodium-sensitive electrode. Thesecan be obtained with tips on the order of 1 mm, and even smaller tipsmay be available. If the exclusion zone is large enough, then theelectrode should reveal the spatial distribution of concentration in thevicinity of NAFION. If necessary, the concentration of salt could bereduced to expand the exclusion zone.

In one implementation, an extractor collects water from a narrowannulus, e.g., much narrower than the 100 μm used in one implementationin the lab. This facilitates collection of water in situations in whichthe exclusion zone is much smaller than is the case with microspheres. ANAFION (or equivalent polymer) tube with an array of small holes mayalso be used, so that the relatively sodium-free water exits outside thetube rather than from an annulus within the tube.

Using Electrical Potential to Increase the Size of the Exclusion Zone

Electrical potentials may also be applied to increase the size of theexclusion zone and hence the efficacy of separation. For example, in oneimplementation water molecules migrate toward a negatively charged(cathode) surface. That is, the applied charge enhances the hydrophiliccharacter of the exclusion surface, thereby increasing the region ofpurified water.

In another implementation, a potential difference is applied betweenparallel wires several cm apart in an aqueous mixture, suspension, orsolution. For example, with five volts between the wires, microsphereexclusion may increase to a centimeter or more from the negativeelectrode. With proper choice of material for the wire(s), (e.g.,similar to materials used in maintenance-free auto batteries) bubbles(electrolysis) are virtually absent.

Further Detail

One objective during development was to lay groundwork for an exemplarydevice that can separate salt and other solutes from water. To designsuch a device, we observed that solutes tend to be excluded from thezone adjacent to many hydrophilic surfaces. Solutes observed to beexcluded ranged from micron-sized colloidal solutes, for example, downto small molecular weight dyes. Hydrophilic surfaces that exclude thesesolutes include various hydrogels and polymeric surfaces. Exclusion isseen not only in static situations but also when the aqueous suspensionor solution flows in channels cut inside of gels, and this formed thebasis for several implementations of the exemplary device.

In one implementation, salt water, or otherwise contaminated water,flows into the gel or polymer channel, and the salt moleculesprogressively migrate from the wall toward the channel axis (center ofthe tube).

This concentrated solution in the channel core is discarded or recycled,while the pure water in the annular region (i.e., outer region of thetube lumen) is collected. Variations of the exemplary technique weretested under a series of experimental conditions, in order to optimizepurification and throughput.

In one implementation, as described above, we examined microspheressuspended in aqueous solution in the vicinity of hydrogel surfaces. Themicrospheres translated away from the surface, leaving amicrosphere-free zone that was unexpectedly large relative toexpectations of classical theory (Israelachvili, 1992): depending onconditions, the microsphere-free zone was on the order of 100 μm ormore. Because the depletion of microspheres from the vicinal zone leftpure water, this principle can be applied to the separation of suspendedor dissolved entities, including salt.

An example of this kind of exclusion is shown in FIG. 6. The gel-waterboundaries are the vertically oriented, thin, white lines. (Thevertically oriented fuzzy band to the right of “gel” is an opticalreflection artifact.) Microspheres migrated away from the gel surface,leaving, within minutes, a zone ˜250 μm that was devoid of microspheres.

FIG. 7 shows another example of exemplary solute exclusion. In FIG. 7,the exclusion-inducing surface is again NAFION. FIG. 7 shows atime-dependent buildup of the solute exclusion zone, which typicallygrows in minutes to 0.5 mm or more.

Our subsequent studies have shown the exemplary exclusion methods to begenerally applicable. Exemplary exclusion was observed not only in thevicinity of a series of synthetic and natural hydrogels, but also nearother hydrophilic surfaces including carboxylated monolayers, PEGylatedsurfaces, and biological surfaces (muscle and vascular endothelium). Invarious implementations, excluded species include microspheres of eithercharge polarity, red blood cells, ion-exclusion resin beads,fluorophore-labeled protein (albumin—as shown in FIG. 8), and variouslow molecular weight dyes. FIG. 9, for example, shows the time coursefor exclusion of the fluorophore, sodium fluorescein, in the vicinity ofNAFION.

In both cases in FIGS. 8 and 9, these relatively low molecular weightsolutes are excluded at least qualitatively by an amount similar to themuch larger colloidal microspheres. Thus, the size range of excludedspecies can be broad from micron-sized particles down to smallmolecules. All of these solutes, suspensions, etc., are excluded fromvicinal water, presumably by some surface induced alteration of thatwater. In one implementation, we derived evidence that at least threephysical features of the vicinal water are different from bulk water:NMR hydrogen nuclei relaxation times; ability to support sustainedpotential difference; and sharply diminished infrared radiation from thevicinal water zone.

Considering the broad size range of solutes confirmed to be excluded (12orders of magnitude in mass), molecules beyond this range, i.e., evensmaller than the lowest molecular weight dyes (e.g., mol. wt. 376) canbe excluded as well.

In some experiments, we built polyacrylic acid gels (also some polyvinylalcohol gels) containing long, cylindrical channels, as shown in FIG.10. Solute-containing water is pumped through the channel; or, in thecase of a vertically oriented channel, the suspension can flow by theforce of gravity; external power is then unnecessary. At the entry, thesolute is distributed uniformly over the cross-section. Farther alongthe channel, the solute can be progressively excluded from the zone justinside the gel. With sufficient tube length, the sub-annular region willbe solute free for practical purposes, or, actually solute free given atheoretically long enough tube.

This solute-free water can then be collected using an annular channel1002 whose outer diameter 1004 is equal to the inner diameter of the gel(FIG. 10, right side). The solute-containing water in the collectionzone 1008 is in the center, i.e., inside the annular solute-free zonebeing collected by the annular channel 1002. When the solute-containingwater is in short supply (e.g., the solute is precious), thesolute-containing water can be recovered, so that the process can berepeated in cascading stages.

As shown in FIG. 11, some initial studies were carried out using 1-μmcarboxylate microspheres, easily detectable with a compound microscope.Polyacrylic acid gels were molded to contain a cylindrical channel, 1.6mm in diameter 50 mm long. Using a motor-driven syringe, suspensions ofmicrospheres were driven through the channel. Because the gel was clear,the microspheres within the channel could be easily visualized. Clear,stable, exclusion zones increased with time (and increased faster withsmaller molecular weight substances; see FIGS. 8 and 9), and grew toappreciable size at distances sufficiently far from the entry orifice.From the left, FIG. 11 shows the time course of microsphere distribution45 mm from entry point at various times after exposure to suspension.The gel boundary is the dark region at top. At this low magnification,microspheres are seen as small, uniform dots. On the right in FIG. 11 isseen microsphere distribution and growing exclusion zone ten minutesafter exposure, at successive locations (10 mm, 25 mm, and 45 mm) alongthe channel.

In one implementation, the “solute” is pathogens, to be concentrated foreasier identification. Thus, although an exemplary system can be used toseparate salt from water, it can also be useful for separatingcontaminants from water.

One advantage of the exemplary differential extractor 100 is itssimplicity. Once designed, it can be manufactured inexpensively, easy tokeep functional, and simple to use. Portable units may operate withoutsupply of external electrical power—by using gravity flow. Ingeographical regions of scarce water supply, gray water, e.g., from ashower, can be recycled, making an exemplary apparatus useful in specialenvironments, such as space vehicles or submarines, where water is inshort supply.

NAFION constitutes a powerful exclusion-generating surface in staticsituations, and may be superior for some applications to gels used toobtain results in flow situations such as that of FIG. 10. NAFION, adurable material, is widely used in fuel-cell applications, and can bemicro-machined to contain arrays of micro fluidic channels for quick andeffective separation.

In pursuing salt separation, one challenge is detection of differencesin concentration of ionic species. While microspheres are detectableunder bright field microscopy and fluorophores are detectable underfluorescence microscopy, direct measurements of salt concentration mayrequire sampling of the fluids. One implementation uses a smallcylindrical tube inserted near to and parallel to the (polyacrylic gelsor NAFION) excluding surface. To prevent premature capillary actionwhile the tube is being positioned, the distal end of the tube can betemporarily sealed. Once the tube is in place, the seal is removed; thenfluid flows by capillary action (or can be drawn by a pump if necessary)and collected for later analysis using an osmometer.

In one implementation, the exclusion surfaces of an exemplarydifferential extractor 100 were obtained as follows. Convenient samplesof NAFION are 180-μm-thick sheets, which can be cut for experiments.Polyacrylic acid (PAAc) can be synthesized in the laboratory. Forexample, a solution can be prepared by diluting 30 ml of 99% acrylicacid with 10 ml deionized water. Then, 20 mg N, N′-ethylenebisacrylamideis added as a cross-linking agent, and 90 mg potassium persulfate isadded as an initiator. The solution is vigorously stirred at roomtemperature until all solutes are completely dissolved, and thenintroduced into a chamber 1.5 mm high, in which a 1-mm glass rod, laterremoved for cylindrical channel experiments, is suspended at mid-height.Gelation takes place as the temperature is slowly raised to about 70° C.The temperature is then maintained at 80° C. for one hour to ensurecomplete gelation. Synthesized gels are carefully removed from thecapillary tubes, rinsed with deionized water, and stored in a largevolume of deionized water, refreshed daily, for one week.

Controls can be carried out first to ensure that collection of fluid bythe tube—or even the presence of the tube itself—does not interfere withthe exclusion zone. One technique is to monitor the exclusion-zoneboundary by optical microscopy, using microspheres (1 μm, carboxylate)as markers. Since the microspheres can be easily visualized, this methodalso permits the detection of any convective flows. If the tube itselfcompromises the zone, different materials can be used as alternates.Slow withdrawal of fluid from the exclusion zone typically does notinduce much disturbance; however, if any disturbance is noted, thecollection rate can be slowed until the disturbance becomes negligiblysmall, the tradeoff being increased time required for collection.

To sample from a broader, more representative zone, the tube can besteadily but gently withdrawn parallel to the exclusion surface duringcollection. Again, it may be important to test in the same way as abovewhether withdrawal disturbs the exclusion zone, and if necessary,collected samples can be analyzed for microsphere contamination.

Once the controls confirm the stability of a given implementation,additional controls can be carried out to test the efficacy of sampling.These tests can be carried out on NAFION and polyacrylic acid surfacesexposed to aqueous solutions of small molecular weight dyes. Dyes areordinarily separated out satisfactorily. It is useful to confirm theabsence of dye from drawn samples of different volume. These samples canbe compared against standards in a fluorimeter. This helps to establishthe size of sample volumes required to avoid contamination in thesalt-exclusion processes.

Next, exclusion of salt can be tested. NaCl concentration can be 100 mMto start. The region of the exclusion zone immediately adjacent to theexcluding surface can be sampled first, as this is the region withinwhich salt should be most profoundly excluded. Samples drawn from thisregion can be tested using osmometry. Next, a micrometer drive can beused to translate the tube to a position ˜100 μm more distant from thesurface, and samples can again be collected. The protocol can berepeated at 100 μm intervals in order to obtain a profile of [NaCl] vs.distance from the excluding surface. A priori, in one implementation,undetectably low concentrations continue for a distance of severalhundred micrometers, followed by a rapid falloff at roughly 0.5 mm fromthe surface. If increased measurement resolution seems warranted,smaller collection tubes can be used, and spatial increments can bereduced.

Separation can be implemented at different NaCl concentrations rangingfrom 1 mM up to 1 M (ordinary seawater is 0.4 M to 0.45 M). If increaseddetection sensitivity is required for low concentrations, atomicabsorption spectrometry can be used instead of osmometry—several atomicabsorption spectrometers are satisfactory for use. We have noted adiminution of exclusion-zone size with salt concentration, ˜40%reduction as [NaCl] rose from nominally zero to 100 mM; hence, with theaddition of salt there is a more rapid falloff of separation efficacywith distance from the excluding surface.

The separation of salts other than NaCl is possible too, as water oftencontains a variety of salts other than NaCl, albeit in lower quantity.The exclusion-zone size may be compromised by different salts indifferent ways; i.e., reduction of exclusion-zone size depends on thesalt's position in the Hofmeister series, K+>Na+>Li+>Ca2+. It can beuseful to verify these preliminary observations systematically, and thentest the efficacy of separation of each one of them. Ideally, they canbe separated with much the same efficacy of NaCl; however if these saltscompromise the exclusion zone sufficiently, then collection parametersmay need to be adjusted.

Other relevant variables that may be important to test for theirultimate practical value include above all, temperature and pH. Theformer can be evaluated by using a temperature-controlled stage duringsalt-separation tests, while the latter can be evaluated by adding HClor NaOH to vary the pH between 3 and 12 with continuous pH monitoring.The optimum result reveals the absence of any strong dependence ofeither of these variables on efficacy of separation; however, a noteddependence can be compensated for in the implementation.

In one implementation, the exemplary technique removes sea-salts fromseawater. In one process, Puget Sound seawater (Na+=410 mM) was used,and tests were carried out as above. The goal was Na+ removal effectiveenough to reach EPA drinking-water standards (20 mg/l, or around 0.9 mM)(http://www.epa.gov/safewater/ccl/sodium.html).

In another implementation, the exemplary technique separates bacteriaand viruses from the aqueous mixture, for decontamination applications,in much the same way as salt separation was accomplished above.

Detail of Pathogen Separation

Common bacteria have a size in the micrometer range, some larger; hence,they are detectable by optical microscopy, most clearly using phase orDIC microscopy. Viruses elude practical detection by optical microscopy;hence, they can be labeled with a fluorophore and detected byfluorescence microscopy. Excluding surfaces can be the same as thoseused above, polyacrylic-acid gels, and NAFION. Similar collectionstrategies as used above can be used in this application. Various commonbacteria and viruses were considered, limited to non-pathogenicvarieties such as heat-inactivated samples that require no specialfacilities. Bacteria include: Escherichia coli (HB101) and Pseudomonasaeruginosa purchasable from American Type Culture Collection (Manassas,Va., USA). Viruses include adenovirus, SV40, and influenza availablefrom Virapur (San Diego, Calif., USA). These can be fluorophore labeled.

Different implementations may vary the conditions used for removing thepathogens. The pH can be varied from 3 to 12 with NaOH and HCl withcontinuous pH monitoring, and runs can be carried out at each pH value.Salt concentration can be varied from the low level of pure water, allthe way up to molar values. Temperature can be varied too, as describedabove.

In the case of bacteria, and unlike salt, because the exclusion zone isvisually detectable, the exemplary technique can measure not only theextent of exclusion, but also the rate at which the exclusion zonedevelops.

These measurements are performed by abruptly exposing the exclusionsurface to a suspension of bacteria, and tracking the time course ofexclusion zone development. Such dynamic measurements are importantfeatures to bear in mind when a particular exemplary purification systemis designed. Another aspect to keep in mind is measurement of separationdynamics during flow in cylindrical tubes (FIG. 10, above).

Having established the basic exclusionary features, including how mucheach type of solute is excluded and the magnitudes of the respectiveexclusion zones, the next step is to exploit those features in animplementation. A basic starting point is the implementation ofmicrosphere separation during flow in cylindrical channels that wasdiscussed above.

In one implementation, the channels are easily made: the gel is moldedto contain a cylindrical glass rod, which is removed once the gel hasset. In the case of NAFION, tubular samples with diameter ˜0.5 nm can beobtained from the supplier. Because the NAFION wall is thin, visualizingparticles or fluorescence within the channel should engender no seriousdifficulty.

A syringe pump is used to drive suspensions through the channel(Improved versions of the pump can eliminate residual pulsations andresult in higher precision measurements.) For test purposes, a samplemay be placed on a microscope stage, flow is imposed by the pump, andthe distribution of microspheres is measured at different times at asingle location, and at different positions along the channel Such testsreveal the time- and distance-dependence of exclusion prior tomanufacture of the implementation.

Measurements such as those just described can be carried out ondifferent solutes. Knowing the size of the exclusion zone in staticsituations (FIGS. 6-9) will shortcut the number of trials (e.g., flowrate, channel diameter and length, etc.) required to establishreasonable parameters such as flow rate for separation of salt, as wellas for separation of pathogens.

For effective exclusion, different solutes may require differentphysical and geometric exclusion parameters. However, it may turn outthat a particular set of parameters is acceptable for the exclusion notonly of salt(s), but also of a range of pathogenic substances. In such acase, it may be possible to remove all of these in a single filtrationpass, without requiring multiple stages. FIG. 12 shows a system forcollecting purified water, i.e., a fixture designed to collect effluentfrom a gel separation channel. The collection system is designed tointerface with the exit of the gel-separation unit; in FIG. 10, itcorresponds to the collection zone 1008 on the right. The design in FIG.12 involves a double cylinder, for collection of annular (solute-free)and core (solute-containing) flows; similar to that of FIG. 10. Aninitial design of the unit in FIG. 12 can be made using thin-walledstainless steel tubing. The interface end of the apparatus may beinserted into the end of the gel or NAFION channel. The inner tube or“waste outlet” is designed to catch the solute-containing fluid, and isconnected to an exit tube, which either discards the fluid, or saves itfor recycling. The annular ring between the inner and outer tubeextracts the purified water, which flows out through a side-exit portfor collection.

For both fractions, pumps may be useful to facilitate more rapid flow.Dimensions and materials for effective water collection devices may beoptimized. The size of the inner cylinder is sometimes critical inensuring that the maximum quantity of salt or impurity is removed. Thisfollows for two reasons: (i) the salt-containing zone of the separatormay need to project entirely within the collector's inner cylinder; and,(ii) the exclusion zone might not exclude uniformly, so that, forexample, regions at low radius just beyond the salt-containing zone maystill contain some amounts of salt whereas regions at larger radius maybe truly salt free. Cylinder diameter can be carefully tested for eachsolute of interest. Thus, using a set “standard” for gel-channelconditions, collection ducts with a series of internal diameters can betested to check for optimum efficacy.

It is also useful to check a series of materials other than stainlesssteel, including various nonreactive metals and polymers, as it is notclear a priori whether a hydrophilic or hydrophobic material will resultin optimum collection. Water must flow freely into the tube; yet itshould not stick excessively to the tube's walls. Hence some combinationof hydrophilic and hydrophobic properties may be necessary to optimizethe ability to collect. One important consideration can be thecollection speed in the absence of vacuum pumping. This can be importantin an effort to make the system independent of the need for externalpower.

Optimizing an Exemplary System

If drinking water is to be filtered from pathogenic substances, thentesting should be done on ordinary drinking water to which pathogenshave been added. If purification turns out not to be adequate in thesesituations, then backtracking can obtain adequate purification, e.g., byadding one solute at a time to pure water to determine which may be the“offending” agent.

Testing can also achieve the optimum excluding material. Polyacrylicacid gels and NAFION are good candidates, because they produce abundantexclusion. However, these surfaces are not necessarily optimal for allsolutes, and there are countless other materials that can be customizedfor various solutes. In particular, gels and polymers studied thus farhave been neutral (polyvinyl alcohol) or negatively charged (e.g.,polyacrylic acid). The one positively charged surface (aminatedstyrene-DVB-copolymer) explored briefly gave positive results. Hence, insome cases positively charged gels (e.g., chitosan) may exclude bothpathogenic substances and salt. In such a case, systematic studiesincluding pH dependence can be carried out for optimizing the excludingmaterial. In some instances, complementarity exists between negativelycharged and positively charged surfaces, and the most effectiveseparation may include one layer of each, or some spatial surfacearrangement of positively and negatively charged regions.

Surfaces to be utilized may include functionalized monolayers (SAMS).Monolayer results obtained with exposed carboxyl groups showed ampleexclusion of carboxylate microspheres. The ability to functionalizesurfaces opens many possibilities in terms of ultimate manufacture.

In one implementation, the system is as independent of externalelectrical power as possible. It is also beneficial to balancepurification efficacy with rapid throughput. Rapid throughput impliesdiminishing drag during flow through narrow channels. In oneimplementation, the friction in tubes lined with certain blockco-polymers is massively diminished—by as much as three orders ofmagnitude (Raviv et al., 2003). If these polymers, e.g., PMMA-PSGMA, arealso found to create exclusion zones for a given solute, then it ispossible to achieve reasonable solute separation, while at the same timeachieving substantially enhanced throughput as a result of loweredresistance—driven only by the force of gravity. In that situation, thesystem can operate much like a household water filter, with simplegravity-driven flow.

In one implementation, an exemplary apparatus is created throughmicrofabrication. If the optimum channel size is in the range ofhundreds of microns or less, then microfabrication can create arrays ofchannels. An example is shown in FIG. 13. The top of FIG. 13 is orientedupward, and the rectangles represent the excluding surfaces. Theunpurified water enters at the top, and as it proceeds downward, theexclusion zone grows.

The contaminated water (stippled) exits at the bottom through aconnecting channel. The purified water (clear) enters a collecting duct(broad “U” in diagram). Because identical, slab-like units are stackedupon one another, the U-shaped ducts create channels oriented normal tothe plane of the diagram. Purified water is collected at the ends ofthose channels. Slight tilt out of the plane of the paper can bias theflow in one or the other direction, facilitating collection.

The exemplary array of FIG. 13 can operate purely by gravitational forceor by pumps to facilitate flow.

Exemplary Methods

FIG. 14 shows a representative exemplary method 1400 of separatingcomponents of aqueous mixtures. In the flow diagram, the operations aresummarized in individual blocks. The exemplary method 1400 may beperformed by hardware, such as the exemplary differential extractor 100.

At block 1402, an aqueous mixture (suspension, solution, etc.), isflowed over a hydrophilic surface, i.e., an exclusion surface, or insome cases a hydrophobic surface. Example materials for such anexclusion surface are certain gels, polymers; NAFION, etc.

At block 1404, purified water can be collected in a first region nearthe hydrophilic surface. The exemplary differential extractor 100 mayhave an annular tube that lifts only the purified water.

At block 1404, one or more concentrated non-aqueous components of theaqueous mixture may be collected in a second region beyond the firstregion of the purified water, with respect to the exclusion surface. Theexemplary differential extractor 100 may have a center or core tube thatdraws the concentrated non-aqueous components from the apparatus.

Alternative Implementation

In an alternate implementation, it has been found that solutes wereexcluded from a region just below the top surface of water, at theair-water interface. With a chamber (or tank) made from two large flatpieces of glass separated by 3 mm, a microsphere suspension was added,and the chamber was viewed facing one of the glass pieces. The zone justbeneath the surface began to clear. Within 30 minutes a 2-mm zone(herein referred to as an exclusion zone) was fully devoid ofmicrospheres. The exclusion zone remained devoid of microspheres formany hours. This was not the result of microsphere settling, which tookplace at approximately 24 hours after filling the chamber.

Other implementations to create water separation in an aqueous solutionare described in an article titled “Cylindrical phase separation incolloidal suspensions,” by Kate Ovchinnikova and Gerald H. Pollack(accepted for publication in Physical Review E by the American PhysicalSociety, January, 2009), which is hereby incorporated by reference.

An example diagram 150 of a tank 151 including an aqueous solution withan air layer, a meniscus layer, and bulk water, which may containmicrospheres and is thus labeled “water+microspheres.” The clear zone,corresponds to the exclusion zone 152 is shown in FIG. 15. The exclusionzone 152 has characteristics similar to the exclusion zones describedabove. When the aqueous solution contains microsphere markers, not onlydoes the zone 152 exclude those microspheres, but also its upper regionhas negative potential, much like exclusion zones. Further the solutionremains at constant width even as the upper surface of water is liftedand moved from side to side with a vertically oriented charged rod.Hence, this zone 152 is mechanically cohesive, much like exclusionzones.

The tank 151 may be used for establishing a volume of an aqueous mixturehaving a surface. In addition an apparatus collects water at the surfaceof an aqueous mixture. The apparatus may establish an exclusion zone 152with a depth in the aqueous mixture. In one implementation, theapparatus may collect water at the surface when the depth of the aqueousmixture is greater than approximately four times the depth of theexclusion zone 152, although any depth may be suitable provided thedepth of the aqueous mixture is greater than the depth of the exclusionzone. The aqueous mixture may include a mixture of water, particles andsolutes and includes particles and solutes whose removal is desired. Inone implementation the depth of the exclusion zone 152 is about 2 mm.

A collection apparatus including a tube may collect water and transferthe collected water from a tank 151 to a collecting chamber. Thecollection apparatus may stop collecting when the water in the exclusionzone 152 has been fully transferred from the tank 151 to the collectingchamber. An apparatus may also be provided to admit more mixture to thetank 151 to let the exclusion zone 152 build for later collection.

In another implementation a skimming apparatus (as generally known) thatincludes the tube may continuously skim the exclusion-zone water on thesurface of the aqueous solution or aqueous mixture. A controller to theskimmer may be provided to adjust the collection rate from the tank 151to a collection chamber so that a rate of buildup of water in theexclusion zone 152 and collection of water reach a steady state.

The presence of a solute-exclusion zone at the upper surface of waterprovides an environment in which water can be skimmed off to providepurified water.

In one flow embodiment, a tank's 151 upper zone is connected through adownward slanted tube to a lower collecting chamber. A valve opensperiodically to allow flow from tank 151 to collecting chamber to occur.The tank 151 is then replenished with the aqueous solution.

In another embodiment, an upper zone in tank 151 is set up similar tothe flow embodiment except that a pump is used to facilitate withdrawalof the top layer.

In another embodiment, the upper zone of the tank 151 is set up similarto the flow embodiment except that multiple stages are used to achievefurther purification.

Illustrative Fraction Collection

FIG. 16 is a diagram illustrating principal features of an apparatus1602 for collecting a fraction of a mixture, suspension, or solution ofa polar liquid, according to an embodiment. As used herein, a fractionis defined as a concentration of a mixed component, suspended component,or solute different from other concentrations of the mixed component,suspended component, or solute at different distances from an interface1610 (described below).

A first collector 1604 such as a collection tube is configured tocollect a fraction of a mixture, suspension, or solution of a polarliquid 1606, 1608 at a selected distance at or away from an interface1610 between the polar liquid and air or a hydrophilic surface 1612. Astructure 1605 is configured to hold the first collector 1604 at theselected distance. A first fraction collected from a first region 1608at a first distance at or away from the interface 1610 may comprisesubstantially pure polar liquid. A second fraction collected at a seconddistance away from the interface in the second region beyond a boundary1614 comprises a an increased concentration of a solute or particlecomponent compared to the first fraction. The first region 1608 is alsoreferred to as an exclusion zone that is formed by an interactionbetween the polar fluid 1606, 1608 and the air or hydrophilic surface1612 according to mechanisms described herein. The polar liquid 1606,1608 may be water.

According to an embodiment, the first collector may be held at the firstdistance selected to collect the first fraction comprising substantiallypure polar liquid from the first region 1608 (exclusion zone), as shown.In some embodiments, the first region may extend to a distance of about2 mm from the interface 1610, where it forms the border 1614 with thesecond region.

Alternatively, the first collector may held at the second distancebeyond the boundary 1614 selected to collect the second fractioncomprising the increased concentration of the solute or particlecomponent (configuration not shown). Alternatively a first collector1604 may be held at a first distance selected to collect the firstfraction comprising substantially pure polar fluid from the firstregion, and a second collector (not shown) may be held to collect thesecond fraction comprising the increased concentration of the solute orparticle component from the second region. Alternatively, a largernumber of collectors 1604 may be held to collect various fractions. Suchcollectors 1604 may be configured to each collect potentially adifferent fraction from a different distance from the interface 1610, ormay be configured to collect substantially the same fraction atsubstantially the same distance from the interface 1610.

The structure 1605 may be configured to hold the first collector 1604 ina substantially constant position at or away from the interface 1610between the polar liquid 1606, 1608 and air or a hydrophilic surface1612. For example, the structure 1605 may include a float configured toprovide buoyancy to hold the collector 1604, and/or other associatedhardware or liquid near the surface 1610 or an air 1612 interface.Optionally, the apparatus 1602 may include a vessel (not shown) forholding the mixture, suspension, or solution of the polar liquid 1606,1608.

FIGS. 3, 4, 6, 7, 8, 9, 11, and 15 illustrate sensing or output fromsensing one or more of a position of the interface 1610; a depth of aninterface 1614 between first and second regions corresponding to anexclusion zone 1608 and concentrated phase, respectively; aconcentration of a mixed component, suspended component. Moreover,referring to FIG. 16, a concentration of a mixed component, suspendedcomponent, or solute collected 1624 by the fraction collector 1604through an opening 1622 may be sensed. For example, referring to FIG. 3,the exclusion zone 110 and microspheres 102 (aka, the concentratedphase) are visualized from an optical detection technique, in this casesensing using a focal plane array image sensor coupled to receive animage through microscope optics. Similarly, FIG. 4 (as described byparagraph 38) shows optical absorbance profiles used to characterize anddetermine differences between the exclusion zone (aka, diluted) and theconcentrated phase. Thus, an optical sensor can be used to determine thepresence or absence of a solute or suspension at various locationsrelative to a fraction collector.

Electrical sensing may also be performed to determine characteristicsand location of an interface, exclusion zone, and concentrated or “bulk”phase. For example, the concentration of a salt solution can becorrelated to the electrical conductivity of the solution. Thus anelectrical sensor can be used to determine characteristics and locationof an interface, exclusion zone, and concentrated or “bulk” phase. Sucha sensor may be made to measure presence/absence of a polar liquid,and/or conductivity or resistivity of the polar liquid at variouslocations (e.g., distances from an exclusion zone-forming interface1610) in a solution.

Moreover, as described above, a structure (e.g. including an actuatorsuch as a micrometer drive) to hold and/or move a collection tube 1604.

A sensor 1616 may similarly provide feedback to a control system todetermine a collection location of a collection tube 1604, for exampleto establish or maintain collection of a selected fraction of the polarliquid and mixed, suspended, or dissolved particles or solutes.According to an embodiment, the selected fraction may be substantiallypure polar liquid. According to another embodiment, the selectedfraction may include an enriched concentration of suspended or dissolvedparticles or solutes. Similarly, a sensor 1616 may be used to providefeedback for selecting one or more of a plurality of collectors 1604 forcollection.

Referring to FIG. 16, the structure 1605 may be configured to hold thefirst collector 1604 at an adjustable 1634 distance at or away from theinterface 1610 between the polar liquid and air or a hydrophilicsurface. One or more sensors 1616 may be configured to sense and outputa sensor signal or data corresponding to one or more of a position 1618of the interface between the polar liquid and air or a hydrophilicsurface; a position 1620 of an interface 1614 between the first andsecond regions; a concentration of a mixed component, suspendedcomponent, or solute in the vicinity 1624 of the first collector 1604(and/or any second collector), such as near the intake 1622 of the firstcollector 1604; or a concentration of a mixed component, suspendedcomponent, or solute collected 1626 by the first collector 1604 (and/orany second collector).

A sensor signal or sensor data may be output by the sensor 1616 toprogrammable logic 1628 such as a microcontroller, state machine, PIDcontroller, or other apparatus configured to drive an actuator 1630configured to adjust the position of the first collector 1604 (and/orany second collector) responsive to the sensor signal or data. Forexample, a rate of liquid collection may be decreased or stopped bycontrolling a pump or valve 1632 if a boundary 1614 between theexclusion zone 1608 and bulk fluid containing suspended particles orsolute approaches a location 1620 too close to a liquid intake 1622.Similarly, the distance (depth) of the collector 1602 may be set as afunction of a detected location 1618 of the interface 1610 by actuatingthe position or configuration 1634 of the structure 1605.

The sensor 1616 may use one or more of a variety of technologies tosense conditions relevant to liquid collection by the collector 1604.For example, the sensor may be an optical sensor, an ultrasonic or sonicsensor, or an electrical sensor.

For example, an optical sensor 1616 can measure scattering caused byparticles in the polar liquid 1606, 1608. Additionally or alternatively,an optical sensor 1616 can measure an absorption characteristic of aspectrum of a solute or suspension. Additionally or alternatively, anoptical sensor 1616 can measure specular reflection off an air/liquidinterface 1610, and given a characteristic exclusion zone 1608thickness, one can infer the distance to the bottom 1614, 1620 of theexclusion zone. In systems where the polar liquid is water, theexclusion zone 1608 was found to strongly absorb 270 nanometerultraviolet light. The sensor 1616 can thus measure 270 nanometerabsorption (or another absorption spectrum characteristic of anexclusion zone 1608 of water or another polar liquid), and optionallyone or more reference wavelengths, to determine or infer the presence orthickness of the exclusion zone 1608. Accordingly, one or more opticalcharacteristics may be measured by the sensor 1616 and output used bythe logic 1628 to drive the actuator 1630.

Similarly, electrical characteristics of the exclusion zone 1608 andbulk or component-enriched polar liquid 1606 beyond the border 1614 ofthe exclusion zone may differ. Conductivity or electrical potential may,for example, be sensed by the sensor 1616 at one or more variouslocations 1612, 1618, 1620, 1624, 1626, and output used by the logic1628 to drive the actuator 1630. Alternatively a sonic or ultrasonictransmission or reflection characteristic may be measured by the sensor1616 and output used by the logic 1628 to drive the actuator 1630.

The actuator 1630 may be configured to adjust a pump or valve 1632configured to control a rate of removal of the fraction by the firstcollector 1604. According to an embodiment, adjustment of a pump orvalve 1632 may be used to select between collection by a plurality ofcollectors 1604. Alternatively or additionally, the actuator 1630 may beconfigured to adjust a position 1634 in which the structure 1605 holdsthe collector 1604. The logic 1628 may receive the sensor signal or dataand responsively drive the actuator to establish or maintain a desiredcollection fraction.

CONCLUSION

The foregoing discussion describes exemplary systems and methods forseparating components of aqueous mixtures, suspensions, and solutions.Although the subject matter has been described in language specific tostructural features and/or methodological acts, it is to be understoodthat the subject matter defined in the appended claims is notnecessarily limited to the specific features or acts described above.Rather, the specific features and acts described above are disclosed asexample forms of implementing the claims.

What is claimed:
 1. A method for collecting a fraction of a polar liquidmixture, suspension, or solution, comprising: providing a hydrophilicsurface; receiving, establishing, or accessing a volume of a polarliquid mixture, suspension, or solution in contact with the hydrophilicsurface; allowing an exclusion zone to form adjacent to an interfacebetween the polar liquid mixture, suspension, or solution and thehydrophilic surface; and collecting a fraction of the polar liquidmixture, suspension, or solution at a selected distance from thehydrophilic surface.
 2. The method for collecting a fraction of thepolar liquid mixture, suspension, or solution of claim 1, whereincollecting the fraction includes collecting the fraction at theinterface or from within the exclusion zone.
 3. The method forcollecting a fraction of the polar liquid mixture, suspension, orsolution of claim 2, wherein the collected fraction comprisessubstantially pure polar fluid.
 4. The method for collecting a fractionof the polar liquid mixture, suspension, or solution of claim 1, whereincollecting the fraction includes collecting the fraction at a distancefrom the interface beyond the exclusion zone.
 5. The method forcollecting a fraction of the polar liquid mixture, suspension, orsolution of claim 4, further comprising: collecting a second fraction atthe interface or within the exclusion zone.
 6. The method for collectinga fraction of the polar liquid mixture, suspension, or solution of claim1, wherein the interface is between the polar liquid mixture,suspension, or solution and air.
 7. The method for collecting a fractionof the polar liquid mixture, suspension, or solution of claim 1, whereinthe interface is between the polar liquid mixture, suspension, orsolution and the hydrophilic surface.
 8. The method for collecting afraction of the polar liquid mixture, suspension, or solution of claim1, wherein the polar liquid is water.
 9. The method for collecting afraction of the polar liquid mixture, suspension, or solution of claim1, further comprising: sensing one or more of a position of theinterface, a size of the exclusion zone; or a concentration of a mixedcomponent, suspended component, or a solute in the vicinity in thecollected fraction.
 10. The method for collecting a fraction of thepolar liquid mixture, suspension, or solution of claim 9, furthercomprising adjusting the selected distance or adjusting a rate ofcollection responsive to sensing.
 11. The method for collecting afraction of the polar liquid mixture, suspension, or solution of claim10, wherein adjusting the rate of collection includes stoppingcollection.
 12. The method for collecting a fraction of the polar liquidmixture, suspension, or solution of claim 1, wherein receiving,establishing, or accessing a volume of a polar liquid mixture,suspension, or solution includes holding the volume of the polar liquidmixture, suspension, or solution in a vessel.
 13. The method forcollecting a fraction of the polar liquid mixture, suspension, orsolution of claim 1, wherein the fraction is defined as a concentrationof a mixed component, suspended component, or solute different fromother concentrations of the mixed component, suspended component, orsolute at different distances from the interface.
 14. The method forcollecting a fraction of the polar liquid mixture, suspension, orsolution of claim 1, wherein the exclusion zone extends to a distance ofabout 2 mm from the interface.
 15. The method for collecting a fractionof the polar liquid mixture, suspension, or solution of claim 1, whereinthe volume of the polar liquid mixture, suspension, or solution isreceived, established, or accessed in a substantially continuous flow.16. The method for collecting a fraction of the polar liquid mixture,suspension, or solution of claim 1, wherein the volume of the polarliquid mixture, suspension, or solution is received, established, oraccessed in a batch.